Module 8, 'Nucleophilic acyl substitution', discusses the substitution reactions that can change the 'acyl X' group of carboxylic acid and its derivatives from the basics to details of reaction mechanisms and application to biochemistry and laboratory organic chemistry.These reactions are critical to the biochemistry of small molecules, movement of 2-carbon (acetyl) groups though metabolism - particularly lipid metabolism - and polymerization of amino acids and synthetic fibers. The material presented should allow prediction of reaction mechanism from reactants. Module 8 references chapter 11 of Soderberg found in volume II.
Big ideas:
1. Carboxylic acid derivatives react by Nu: acyl substitution reactions; ‘acyl X’ is the LG. 2. Carboxylate must be activated by phosphorylation in order to undergo Nu: acyl substitution. Module 8 slide sets: Nucleophilic acyl substitution reactions
(Click on the links below to download each slide set for the lecture.) Introduction: Discovery of penicillin 8.1: Carboxylic acid derivatives 8.2: The nucleophilic acyl substitution mechanism 8.3: The relative reactivity of carboxylic acid derivatives 8.4: Acyl phosphates 8.5: Formation of thioesters, esters, and amides 8.5A: Thioester formation 8.5B: Ester formation 8.5C: Amide formation 8.6: Hydrolysis of thioesters, esters, and amides 8.7: Protein synthesis on the ribosome 8.8: Nucleophilic substitution at activated amides and carbamides 8.9: Nucleophilic acyl substitution reactions in the laboratory 8.9A: Ester reactions: bananas, soap and biodiesel 8.9B: Acid chlorides and acid anhydrides 8.9C: Synthesis of polyesters and polyamides 8.9D: The Gabriel synthesis of primary amines 8.10: A look ahead: acyl substitution rxns w/ carbanion or hydride ion Nu: Resources for students:
> Module 8 lecture outline (PDF) > Module 8 lecture with instructor's notes (PDF) > Module 8 key concepts > Module 8 practice problems > Practice problems KEY > Video tutorials for Module 8:
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*Assignments:
> Homework set 8 |